Stabilization of rubberlike copolymers with reaction products of sulfur dichloride, an aldehyde, and a phenol



Patented July 20, 1948 STABILIZATION OF RUBBERLIKE COPOLY- MERS WITH REACTION PRODUCTS OF SULFUR DICHLORIDE, AN ALDEHYDE, AND

A PHENOL Gordon W. Gottschal k, Akron, Ohio, assignor to r The Firestone Tire & Rubber Company, Akron, Ohio, a corporation of Ohio No Drawing. Application April 5, 1946,

y Serial No. 659,895

, 13 Claims.

1 This inventionrelates to improved synthetic rubber compositions and methods of using the same. More particularly, it relates to resins prepared from sulfur dichloride, a substituted phenol, and an aldehyde, and to the use of such resins to impart tack to uncured, rubber-like copolymers of a conjugated diene,fr example, butadiene, isoprene, Z-cyanobutadiene, cyclopentadiene, methylpentadiene, piperylene, dimethylbutadiene, etc-and a vinyl aromatic compoundfor example, styrene, alpha-methylstyrene, nuclearsubstituted styrenes, monochlorostyrene, dichlorostyrene, vinylnaphthalene, vinylbiphenyl, vinylcarbazole, 2-vinyl-5-ethyl-pyridine, 2-ethyl-5- vinylpyridine, etc. The tackifier may advantageously be employed with a rubber-like copolymer formed in the presence of rosin soap, or other tackifying material added in other ways. The invention will be described more particularly as it relates to the rubber-like copolymer of butadiene and styrene known as GR-S.

- Difliculty has been experienced in the mechanical processing of GR-S because it does not naturally have the tack that natural rubber possesses. For example, when natural rubber is used in building a tire, the various plies of fabric treated with the uncured rubber readily adhere to one another when touched together or pressed together by hand. Furthermore, the tread stock which contains no fabric is sufliciently tacky so that it retains its place when merely pressed into position. The various parts of a tire prepared with uncured natural rubber, when assembled, adhere to one another so that the green tire produced by pressing together the uncured parts will withstand rather rough handling without damage.

The use ofGR-S in tires has necessitated a change in the handling procedure because the rubber-like copolymers of butadiene and styrene (GR-S) are nottacky. Rough handling causes the plies to separate, and separations and failures in the cured tire may result from lack of tack in the GR-S stock used in building the tire.

According to the present invention, tack is imparted to rubber-like copolymers of butadiene and styrene, etc, by the incorporation therein of a 'resin from a hydrocarbon-substituted phenol, an aldehyde, and sulfur dichloride. Such tackifiers incorporated in the uncured stock give tack without adversely effecting the properties of the cured rubber obtained therefrom, and the degree of tack given the GR-S, etc., may approach that of natural rubber. The tackifier may be incorporated into GR-S stocks used for coating fabric, forming tire treads, etc., to impart sufiicient tack to these tire component parts to permit them to be used in building tires in the same manner as was previously employed with natural rubber stocks.

Various experiments have been made with the use of this type of tackifier in uncured, rubberlike copolymers of a conjugated diene and a vinyl aromatic compound. The products produced by an alkali-catalyzed aldehyde reaction are preferred to the acid-catalyzed materials, which produce less tack. In recording the results of the experiments in the following tables, the tack of copolymers which are completely lacking in tackiness is rated as 0, and the tackiness of milled, uncured natural rubber is rated as 10. Two sheets having such high tackiness of 10, when pressed together, have sufilcient adherence that tears may occur when an effort is made to separate them. The closer the tack number approache 10, the better the tack.

The tackiilers may be produced by first reacting the aldehyde and phenol (alkali catalyzed) and then treating the product with sulfur dichloride; or by first reacting the phenol with sulfur dichloride and then obtaining an aldehyde reaction product (alkali catalyzed) therefrom. The following examples are illustrative:

EXAMPLE 1 Seventy-five grams of para-tertiary-butylphe- 1101 were added to 37.5 grams of 40 per cent Formalin (aqueous formaldehyde). Forty grams of a 10 per cent solution of sodium hydroxide were then added and the mixture stirred for 15 hours at 25 C. The mixture was neutralized with acetic acid and taken up in ethylene dichloride. The bulk of the water was removed by decantation, and the remainder was distilled off with some of the solvent until a clear distillate was observed. The dried product was diluted with ethylene dichloride until a solution was obtained that contained approximately 20 per cent of the phenolformaldehyde reaction product. There was added to this solution at the reflux temperature of the solvent 28.4 grams of sulfur dichloride dissolved in an equal volume of ethylene dichloride. The addition of the sulfur dichloride was made over a one-half-hour period, and the refluxin was continued for one and one-half hours following this addition. The solvent was removed on a steam bath under reduced pressure. The produce is a dark brown resin with a softenini Point of 6383 C. The yield was 86.9 grams.

.sodium hydroxide solution. This mixture was stirred vigorously at 25 C. for one hour and then at 70 C. for three more hours. The mass was cooled and the water layer discarded. The solution was then heated under reduced pressure and the solvent removed up to a temperature of 100 C. The product, a hard, yellow resin which fused in the flask, was dug out. It has a softening and decomposition point of approximately 240-260 C. The yield was 81.5 grams.

Exams: 3

Seventy-five grams of para-tertiary-butylpheno], 43 grams of 35 per cent Formalin, and 40 grams of 20 per cent sodium hydroxide were heated under reflux with stirring at 85-95 C. for three and a half hours. The viscous syrup was poured into cracked ice in a mortar and pulverized. The mass was neutralized with 8 milliliters glacial acetic acid, washed several times with ice water, and filtered. Weight 140 grams.

The resin was placed in a' flask and dissolved in 600 grams of ethylene dichloride by gently warming. Forty grams of water were removed by decantation, and a small amount of the solvent was distilled to remove the last traces of water.

The solvent was replaced, and to the stirred mixture at the reflux temperature was added a 50 per cent ethylene dichloride solution of sulfur dichloride containing 46.4 grams of the latter. The addition was made over a one-half-hour period. Refluxing was continued for one and a half hours. The solvent was removed on the steam bath under vacuum. The result was 110 grams of a clear brown resin which softened between 80-110 C.

Exaurn: 4

One hundred grams of a para-tertiary-butylphenolacetaldehyde resin (softening point 75-78 C.) were dissolved in 400 grams of ethylene dichloride, and to this refluxing solution there were added, over a,45-minute period, 6.0 grams of sulfur dichloride dissolved in an equal weight of ethylene dichloride. Refluxing was continued for one and one-half hours, and the solvent was removed on the steam bath under reduced pressure. The resin is amber to brown in color and has a softening range from 85-100 C.

Exsurnr: 5

Para-tertiary-decyiphenol (46.8 grams), 15.0 grams of 40 per cent formaldehyde, and 20.0 grams of per cent sodium hydroxide were stirred for 17 hours at C. The reaction mixture was neutralized with acetic acid. The decyiphenolformaldehyde product was dissolved in 250 grams of ethylene dichloride and distilled until dry. The solvent was replaced, and 17.9 grams of sulfur dichloride dissolved in 20 grams of ethylene dichloride were added over a one-half-hour period at the reflux temperature of the mixture. Refluxing was continued for one hour, and the solvent was then removed on the stem bath under reduced pressure. The product is a dark brown, soft resin which softens between and 0.

Eighty-two grams of ortho-tertiary-amylphenol were added to 37.5 grams of 40 per cent Formalin. Forty grams of a 10 per cent aqueous solution of sodium hydroxide were then added, and the mixture was stirred at room temperature for 18 hours. The reaction mixture was neutralized with acetic acid. The product was taken up in ethylene dichloride and dried by decantation and the distillation of a small amount of the solvent.

A solution of such amylphenol-formaldehyde reaction product was adjusted to contain 53 grams of'reaction product 111.215 grams of ethylene dichloride. To this-refluxing solution there was dropped, during the course of 30 minutes, a 50 cent solution of 25.9 grams of sulfur dichloride in ethylene dichloride. The refluxing was continued for 2 hours to remove hydrogen chloride from the mixture, and then the solvent was distilled on a, steam bath and under reduced pressure. softening point of 60-80 C. The yield was quan- The product is a soft, dark resin with a p-Cyclohexylphenol p-Tertiary-butyl-m-cresol p-Hexyiphenol p-Heptylphenol p-n-Amylphenol p-Secondary-butyl-m-creso p-n-Butylphenol p-Neopentylphenol p-Phenylphenol p-Isoamylphenol p-(1,1,3,3-tetramethylbutyl) phenol p-Isopropylphenol o-Amylphenol o-Butylphenol o-(Z-heptyl) phenol o-Cyclohexylphenol o-Phenylphenol The aldehydes which may be employed include formaldehyde, acetaldehyde, and giyoxal.

Experiments showed that improved tack was obtained when the uncured copolymer was compounded with a softener, such as a coal-tar oil, pine tar, dipentene, etc. The addition of a compound such as zinc resinate (or zinc rosinate) improved the tack. The tackifier may be added to the latex or may be compounded on a mill or in an internal mixer. It is necessary to obtain a certain amount of solution in the copolymer, but any means of accomplishingthis-whether or not associated with other compounding ingredients and whether or not heat is applied-is satisi iii 'y- 5 y 6 The first table gives the tack rating of aco- T Me polymer (on-s) obtained from '15 parts of butadiene and 25 parts of styrene with 10' parts of each of the two resins prepared according to cmmmw Examples 1 and 2 per 100 parts of Git-8: g rm 9 bl 1 Formula z''riiil'Zfib'iiilh' 1 Formula: 8 Iormula 3.oontrol (no taokiiier) -1 Tackiiier Tack Rating 0 10 b The tackiflers of Examples and 6 were tested y mixing parts with 100 parts of GR-S. The

l h 1- n 11 11110- 352 i3ciiottt5ir2t'&?;t%liif-fff.-f... as results are givenin the following table: p tertiary butyiphenoi sulfur dichloride iormalde hydo reaction product (Example 2) 6 Table V A copolymer of butadiene and styrene obtained 1 Tackiiier I Tack listing in an emulsion containing rosin soap wa c pounded according to the following formula: 0

Formula 1 Parts Oopolymer 50.00 Tackifler 2.50 Pine tar 1.251 Dipentene 1.50

The tackiflers of Examples 1 and 2 were compounded in this formula. The products were tested with the following results:

Table II Tack iiier Tack Rating none but containing pine tar and dipentene) 2 ptertiary-butylphenol-iormaldehyde-suliur dichloride reaction product (Example 1) 7-8 p tertiary butylphenol sulfur dichloride iormaldehyde reaction product (Example 2) 6 Softeners improve the tack, particularly in the case of high-melting tackiilers, by aiding the solution of the tackifler in the copolymer.

The following table records the results obtained by adding to 100 parts of GR-S 10 parts of the tackiiler oi Example 4:

Table III Tackiiier Tack Rating none 0 p-tertiary-butylphenol-acetaldehyde-sulfur dichloride reaction product 6-7 The tackifier of Example 3 was compounded according to different formulae and then tested for It is recognized that channel black reduces tack, and the results of the experiment are recorded to show that even'in the presence of this much black, the compound still had good tack. The results of the tests are recorded in the following table:

none p-tertisry-decylphenol-iormaldehyde-suliur dichloride reaction product (Example 5) 4 o-tertiary-amylphenol-iorma dehyde-suliur dichloride reaction product (Example 6) 5 GR-S latex cements (aqueous dispersions) and ordinary solvent cements of GR-S type synthetic rubbers are notoriously poor in adhesive proper-v ties.- However, when such cements contain a tackiiier in accordance with the present invention, the cements exhibit substantially improved powers of adhesion, approaching conventional natural rubber cements in this respect.

The invention is not limited to the formulae disclosed or to other details of the disclosure. Modifications may be made without departing from the scope of the appended claims.

What I claim is:

l. Tacky, uncured, rubber-like composition composed of copolymer of a conjugated diene and a vinyl aromatic compound which includes as a tackifier a reaction product of (1) sulfur dichloride. (2) an aldehyde of the class consisting of formaldehyde, acctaldehyde, and giyoxal, and (3) a phenol of the class consisting of phenols substituted in ortho position and phenols substituted in the para position, the substituent being a hydrocarbon radical containing three to ten carbon atoms, the aldehyde reaction being alkalicatalyzed.

2. Tacky, uncured, rubber-like composition composedessentially of butadiene-styrene copolymer which includes as a tackifier a reaction product of (1) sulfur dichloride, (2) an aldehyde of the class consisting of formaldehyde, acetaidehyde, and glyoxal, and (3) a phenol of the class consisting of phenols substituted in ortho. position and phenols substituted in the para position, the substituent being a hydrocarbon radical containing three to ten carbon atoms, the aldehyde reaction being alkali-catalyzed.

3. A tacky composition which contains rubberlike copolymer of butadiene and styrene and a tackiiier which is the sulfur dichloride reaction product of a product obtained by the alkalicatalyzed reaction of formaldehyde and an alkylphenol having para to the hydroxyl group an product of sulfur dichloride and an alkyiphenol which contains in the position para to the hydroxyl group an alkyl group containing four to seven carbon atoms.

6. A tacky composition which contains uncured, rubber-like copolyiner of butadiene and styrene and as a tackifier the sulfur dichloride reaction product of the alkali-catalyzed reaction product of formaldehyde and para-branched-chain-butylphenol.

'7. A tacky composition which contains uncured, rubber-like copolymer of butadiene and styrene and the alkali-catalyzed formaldehyde reaction product of the reaction product of sulfur dichloride and para-branched-chain-butylphenol.

8. A tacky composition which contains uncured, rubber-like copolymer of butadiene and styrene and the alkali-catalyzed formaldehyde reaction product of the reaction product of sulfur dichloride and para-branched-chain-amylphenol.

9. A tacky composition which contains uncured, rubber-like copolymer of butadiene and styrene and as a tackifier the sulfur dichloride reaction product of the alkali-catalyzed reaction product of acetaldehyde and para-branched-chain amylphenol.

10. A tacky composition which contain uncured, rubber-like copolymer of butadiene and styrene and the alkali-catalyzed acetaldehyde reaction product of the reaction product of sulfur dichloride and para-branched-ch'ain-amylphenol.

11. The process of imparting tack to parts formed of rubber-like copolymer of a conjugated diene and a vinyl aromatic compound and producing an article therefrom which comprises incorporating in the copolymer from which the parts are made sufllcient tackifier to cause the parts to cohere when brought in contact, forming the green article from the parts, and then vulcanizing; the tackifler being the reaction product of (1) sulfur dichloride, (2) an aldehyde of the class consisting of formaldehyde, acetaldehyde, and glyoxal, and (3) an alkylphenol which contains in the position para to the hydroxyl group an alkyl group. containing four .to seven catalyzed.

12. The process of imparting tack to parts formed of rubber-like butadiene-styrene copolymer and producing an article therefrom which comprises incorporating in the copolymer from which the parts are made sufficient tackifler to cause the parts to cohere when brought in contact, forming the green article from the parts, and then vuicanlzing; the tackifier being the alkali-catalyzed reaction product of an aldehyde of the class consisting of formaldehyde, acetaldchyde, and glyoxal, on the reaction product of sulfur dichloride and a p-alkylphenol in which the alkyl group is a branched-chain alkyl group which contains four to seven carbon atoms.

13. The process of imparting tack to parts formed of rubber-like butadiene-styrene copolymerand producing an article therefrom which comprises incorporating in the copolymer from which the parts are made sufiicient tackifier to cause the parts to cohere when brought in contact, forming the green article from the parts, and then vulc-anizing; the tackifier being the sulfur-dichloride reaction product of the alkali-catalyzed reaction product of an aldehyde of the class consisting of formaldehyde, acetaldehyde, and glyoxal and a p-alkylphenol in which the alkyl group is a branched-chain alkyl group which contains four to seven carbon atoms.

GORDON W. GOTTSCHALK.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Germany July 14, 1927 

